Curable Compositions Of Benzoxazine And Phthalonitrile Resins

ABSTRACT

The present disclosure provides a polymerizable thermosetting composition comprising an acetylene-bearing benzoxazine compound and a phthalonitrile monomer. The composition can provide a low viscosity for RTM application and can fully cured at a much lower temperature than the phthalonitrile monomer. The cured thermoset polymers having excellent thermal and mechanical properties, such as high thermal stability, heat resistance, high char yield, and enhanced structural rigidity.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Patent Application Ser. No. 62/928,466, filed Oct. 31, 2019, the entire contents of which are expressly incorporated herein by reference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not applicable.

FIELD

The present disclosure generally relates to a polymerizable thermosetting composition comprising a phthalonitrile monomer and an acetylene-bearing benzoxazine compound, and their use for applications in various industries, such as, but not limited to, the building and construction, electronics packaging, energy and power generation, aerospace, transportation and medical device industries.

BACKGROUND

Phthalonitrile monomers are a new class of high-performance monomers developed for high temperature applications, such as in the production of prepregs, laminates and structural composite parts. For example, U.S. Pat. Nos. 6,420,464, 8,039,576, 8,853,343, 9,920,165 and US Pat. Publ. No. 2019/0047946 disclose various phthalonitrile monomers derived from phenols, aromatic diols reacted with diphenyl acetylenes, polyphenols from renewable sources, and bisphenols. These phthalonitrile monomers, after curing, have been found to possess excellent thermal and thermo-oxidative stability with initial decomposition temperatures greater than 450° C., as well as a myriad of other highly attractive performance properties, such as enhanced flame-resistance, the absence of a glass transition temperature before thermal decomposition, good mechanical properties at high temperatures, low water uptake, excellent corrosion resistance and advanced UV-shielding behavior.

However, state of the art phthalonitrile monomers are known to suffer from brittleness due to the rigidity of the monomeric precursors and the high degree of cross-linking in the final cured product. Additionally, these phthalonitrile monomers are generally solid at room temperature and therefore must be melted prior to use. Moreover, they can require higher than desired curing temperatures (for e.g. above 250° C.) and longer times to fully cure.

To overcome these drawbacks, attempts have been made to adjust the chain length of the moieties between the phthalonitrile monomer units in order to reduce their melting point and improve the flexibility of the cured product. Different types of catalysts have also been used to improve the curing behavior of these phthalonitrile monomers. Finally, in order to improve the processability, curing behavior and final properties of the cured phthalonitrile product, U.S. Pat. No. 5,939,508, WO 2017105890 disclose particular phthalonitrile monomers copolymerized with an epoxy or benzoxazine resin; however, such compositions can still require higher than desired curing temperatures (e.g., well above 250° C.) and longer times to fully cure, and have insufficient char yield for carbon-carbon composite applications.

It would be desirable to further improve the curing cycle in the copolymerization of thermosetting compositions that exhibit even better processability and curing behavior and produce cured products having improved thermal and mechanical properties.

SUMMARY

The present disclosure generally provides a polymerizable thermosetting composition comprising (i) an acetylene-bearing benzoxazine compound, and (ii) a phthalonitrile monomer.

The polymerizable thermosetting compositions of the present disclosure may be cured to form thermoset polymers having improved thermal and mechanical properties. Accordingly, the polymerizable thermosetting compositions can find use in a variety of applications, such as, but not limited to, the building and construction, electronics packaging, military, energy and power generation, aerospace, transportation and medical device industries.

DETAILED DESCRIPTION

The present disclosure generally provides a polymerizable thermosetting composition comprising (i) an acetylene-bearing benzoxazine compound and (ii) a phthalonitrile monomer. It has been surprisingly found the composition of the present disclosure has a faster cure over other state of the art benzoxazine/phthalonitrile compositions at comparable conditions. For instance, the presently disclosed composition may require a staged cure at a temperature up to 200° C. to 220° C. followed by a post-cure at a temperature ranging from 250° C. to 260° C. By comparison, a phthalonitrile monomer, alone, generally requires a curing temperature of at least 350° C. (See Example 3-8) for homopolymerization without any catalyst. The phthalonitrile monomer is capable of cross-linking with the acetylene functional group in the acetylene-bearing benzoxazine compound, resulting in improved thermal and mechanical properties, such as an increase in thermal stability, heat resistance, char yield, and enhanced structural rigidity. Not to be limited to a particular theory, it is thought that the high enthalpy (e.g., over 800 J/g) of the acetylene-bearing benzoxazine compound provides sufficient heat to promote the polymerization of the phthalonitrile monomer. At the same time, the acetylene-bearing benzoxazine compound also has the capability to dissolve a certain amount of the phthalonitrile monomer at about 20-40° C. below the melting point of the phthalonitrile monomer, resulting in a mixture having a low viscosity that can be easily processed by infusion applications, among other applications.

The following terms shall have the following meanings:

The term “comprising” and derivatives thereof are not intended to exclude the presence of any additional component, step or procedure, whether or not the same is disclosed herein. In order to avoid any doubt, all compositions claimed herein through use of the term “comprising” may include any additional additive or compound, unless stated to the contrary. In contrast, the term, “consisting essentially of” if appearing herein, excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those that are not essential to operability and the term “consisting of”, if used, excludes any component, step or procedure not specifically delineated or listed. The term “or”, unless stated otherwise, refers to the listed members individually as well as in any combination.

The articles “a” and “an” are used herein to refer to one or more than one (i.e. to at least one) of the grammatical object of the article. By way of example, “a functionalized phthalonitrile monomer” means one functionalized phthalonitrile monomer or more than one functionalized phthalonitrile monomer.

The phrases “in one aspect”, “according to one aspect” and the like generally mean the particular feature, structure, or characteristic following the phrase is included in at least one aspect of the present disclosure and may be included in more than one aspect of the present disclosure. Importantly, such phases do not necessarily refer to the same aspect.

If the specification states a component or feature “may”, “can”, “could”, or “might” be included or have a characteristic, that particular component or feature is not required to be included or have the characteristic.

According to one aspect, the present disclosure provides a polymerizable thermosetting composition comprising an acetylene-bearing benzoxazine compound and a phthalonitrile monomer.

Such acetylene-bearing benzoxazine compounds are described in WO 1999/18092, the contents of which are incorporated herein by reference. In particular, the acetylene-bearing benzoxazine compound may be prepared from the reaction of a monophenolic compound, an aldehyde and a primary amine.

The monophenolic compounds are, such as, but not limited to, phenol, cresol, 2-bromo-4-methylphenol, 2-allylphenol, 1,4-aminophenol and the like. In one embodiment, the phenol-type compound is phenol or allylphenol.

The aldehyde compound may be, but is not limited to, formaldehyde, paraformaldehyde, polyoxymethylene or a compound having the formula R_(a)CHO where R_(a) is a C₁-C₁₂ aliphatic group. In one embodiment, the aldehyde compound is formaldehyde.

The primary amine may be an amine having from 2-40 carbons with one or more carbon to carbon triple bond groups and optionally an O, N, S or halogen heteroatom. Intermediate between the nitrogen of the primary amine and the carbon to carbon triple bond group optionally can be a C₁-C₆ alkyl group optionally substituted with an aromatic group having 6-12 carbons or an aromatic group having 6-12 carbons optionally substituted with a C₁-C₆ alkyl group. The carbon to carbon triple bond group includes those having the formula —C≡CR_(d),-CH₂—C≡CR_(d),

where R_(d) is hydrogen, a C₁-C₅ alkyl group optionally substituted with an aromatic group having 6-12 carbons or an aromatic group having 6-12 carbons optionally substituted with a C₁-C₅ alkyl group. In one particular embodiment, the primary amine having one or more carbon to carbon triple bonds is 3-aminophenylacetylene and propargylamine.

In one embodiment, the one or more acetylene-bearing benzoxazine compounds are represented by the following structure:

wherein: each of R₁, R₂, R₃, R₄, and R₅ is independently selected from a hydrogen atom, a substituted or unsubstituted C₁-C₂₀ alkyl group, a substituted or unsubstituted C₂-C₂₀ alkenyl group, a substituted or unsubstituted C₆-C₂₀ aryl group, a substituted or unsubstituted C₂-C₂₀ heteroaryl group, a substituted or unsubstituted C₄-C₂₀ carbocyclic group, a substituted or unsubstituted C₂-C₂₀ heterocyclic group, or a C₃-C₈ cycloalkyl group; b is an integer ranging from 1 to 4, wherein: when b is 1, Z is a hydrogen atom, a substituted or unsubstituted C₁-C₂₀ alkyl group, a substituted or unsubstituted C₂-C₂₀ alkenyl group, a substituted or unsubstituted C₆-C₂₀ aryl group, a substituted or unsubstituted C₂-C₂₀ heteroaryl group, a substituted or unsubstituted C₄-C₂₀ carbocyclic group, a substituted or unsubstituted C₂-C₂₀ heterocyclic group, or a C₃-C₈ cycloalkyl group; each R₁ is an alkynyl substituted C₁-C₂₀ alkyl group, an alkynyl substituted C₈-C₂₀ aryl group, an alkynyl substituted C₂-C₂₀ heteroaryl group, an alkynyl substituted C₄-C₂₀ carbocyclic group, an alkynyl substituted C₂-C₂₀ heterocyclic group, or an alkynyl substituted C₃-C₈ cycloalkyl group; when b is 2, Z is a direct bond or a substituted or unsubstituted C₁-C₂₀ alkyl group, a substituted or unsubstituted C₂-C₂₀ alkyl group, with aryl or heteroaryl bridge, a substituted or unsubstituted C₂-C₂₀ alkenyl group, a substituted or unsubstituted C₂-C₂₀ alkynyl group, a substituted or unsubstituted C₆-C₂₀ aryl group, a substituted or unsubstituted C₂-C₂₀ heteroaryl group, O, S, S═O, O═S═O, C═O, or C═CCl₂; and when b is 3 or 4, Z is a substituted or unsubstituted C₁-C₂₀ alkyl group, a substituted or unsubstituted C₂-C₂₀ alkyl group, with aryl or heteroaryl bridge, a substituted or unsubstituted C₂-C₂₀ alkenyl group, a substituted or unsubstituted C₂-C₂₀ alkynyl group, a substituted or unsubstituted C₆-C₂₀ aryl group, a substituted or unsubstituted C₂-C₂₀ heteroaryl group; and when b is 3 or 4, Z is a substituted or unsubstituted C₁-C₂₀ alkyl group, a substituted or unsubstituted C₂-C₂₀ alkyl group, with aryl or heteroaryl bridge, a substituted or unsubstituted C₂-C₂₀ alkenyl group, a substituted or unsubstituted C₂-C₂₀ alkynyl group, a substituted or unsubstituted C₆-C₂₀ aryl group, a substituted or unsubstituted C₂-C₂₀ heteroaryl group; and each R₆ is an alkynyl substituted C₁-C₂₀ alkyl group, an alkynyl substituted C₈-C₂₀ aryl group, an alkynyl substituted C₂-C₂₀ heteroaryl group, an alkynyl substituted C₄-C₂₀ carbocyclic group, an alkynyl substituted C₂-C₂₀ heterocyclic group, or an alkynyl substituted C₃-C₈ cycloalkyl group.

In one particular embodiment, the acetylene-bearing benzoxazine compound is phenol 3-aminophenyl acetylene benzoxazine or 2-allylphenol 3-aminophenyl acetylene benzoxazine.

The phthalonitrile monomer is obtained from the reaction of (i) a multifunctional phenolic compound, and (ii) 4-nitrophthalonitrile.

The multifunctional phenolic compound may be, but is not limited to, resorcinol, bisphenol A, bisphenol C, bisphenol F, bisphenol E, bisphenol S, 2,2′,6,6′-tetramethylbisphenol F, 1,2,2,2-tetraphenolethane, thiodiphenol, phenolphthalein, dicyclopentadienyidiphenol, 1,8-hydroxyanthraquinone, 1,6-dihydroxynaphthalene, 2-2′-dihydroxyazobenzene, 1,3,5-trihydroxybenzene, and a polyhydric phenol compound comprising at least one furan group or thiophene group.

In one particular embodiment, the multifunctional phenolic compound is selected from bisphenol M, bisphenol A, bisphenol C, bisphenol P, 2,2′,6,6′-tetramethylbisphenol F, or furanyl-substituted 2,2′,6,6′-tetramethylbisphenol F.

The polyhydric phenol compound comprising at least one furan group or thiophene group, includes those compounds derived from a phenol compound and a compound of the formula (1)

where X is oxygen or sulfur, Q is hydrogen or a C₁-C₅ alkyl group and j is an integer of 1 to 3. Such compounds of formula (1) include, but are not limited to, furfural, 3-furaldehyde, 3-methylfurfural, 5-methylfurfural, 5-ethylfurfural, 2-thiophene-carboxyaldehyde, 3-thiophene-carboxyaldehyde, 3-methyl-2-thiophene-carboxyaldehyde and the like.

The phenol compound can include, but is not limited to, phenol, cresol, xylenol (dimethylphenol) such as 2,6-xylenol, trimethylphenol, 2,5-alkylphenol, such as 2-tert-butyl-5-methyl-phenol or 2-tert-butyl-4-methylphenol, allylphenol, alkynyl phenol, octylphenol, phenylphenol, diphenylphenol, guaiacol, hydroquinone, resorcinol, catechol, naphthol, dihydroxynaphthalene, methyl naphthol, bisphenol A, bisphenol F and the like.

The polyhydric phenol compound comprising at least one furan group or thiophene group may be prepared by methods generally known to those skilled in the art. For example, the phenol compound may be condensed with the compound of formula (1) in the presence of a base and optionally an alcohol or mono-substituted benzene at a temperature of between about 30° C. to about 150° C., or between about 60° C. to about 90° C. In general, the amount of the phenol compound and the compound of formula (1) present during condensation may range from between about 1.5 moles to about 20 moles of the phenol compound per 1 mole of the compound of formula (1). In some embodiments, the amount of the phenol compound to the compound of formula (1) present during condensation may range from between about 1.8 moles to about 10 moles of the phenol compound per 1 mole of the compound of formula (1).

Examples of bases which can be used include, but are not limited to, alkaline metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.; alkaline earth metal hydroxides, such as magnesium hydroxide, calcium hydroxide, etc.; alkaline metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, potassium-tert-butoxide, etc.; and alkaline earth metal alkoxides, such as magnesium methoxide, magnesium ethoxide, etc. These bases can be used alone or in combination of two or more. The base may be used in an amount of between about 0.005 moles to about 2.0 moles per 1 mole of the phenol compound, or between about 0.01 to about 1.1 moles per 1 mole of the phenol compound.

The alcohol or mono-substituted benzene solvents which may be used include, but are not limited to, methanol, ethanol, propanol, isopropanol, toluene, xylene and the like, which can be used alone or as a mixture. When required, such solvents may be used in an amount of between about 5 parts by weight to about 500 parts by weight per 100 parts by weight of the phenol compound, or between about 10 parts by weight to about 300 parts by weight per 100 parts by weight of the phenol compound.

The reaction may be carried out by adding the base to a mixture of the phenol compound and the compound of the formula (1) (and optionally alcohol or mono-substituted benzene solvent) and heating the resulting mixture. Alternatively, the compound of formula (1) may be added to a mixture of the phenol compound and the base (and optionally alcohol or mono-substituted benzene solvent) under heating. The reaction time may range from between about 5 hours to about 100 hours. After the reaction has run to completion, the reaction mixture may be neutralized. Any unreacted materials may be subsequently removed by filtration or by heating in vacuum.

According to one embodiment, the polyhydric phenol compound comprising at least one furan group or thiophene group is a compound selected from the formulas (2) to (10)

where n is an integer from about 3 to about 3.2.

In still another embodiment, the polyhydric phenol compound comprising at least one furan group or thiophene group is derived from bisphenol A or bisphenol F and the compound of formula (1) where X is oxygen and Q and j are defined as above.

According to one embodiment, the phthalonitrile monomer is formed by reacting the multifunctional phenolic compound with 4-nitrophthalonitrile in the presence of a catalyst and optionally a solvent.

Examples of catalysts include, but are not limited to, the bases described above, as well as alkali metal salts, such as cesium carbonate, potassium carbonate or sodium carbonate, organolithium reagents, such as methyl or n-butyl lithium, Grignard agents, or any combination thereof.

Examples of solvents which may be used include, but are not limited to, any polar or nonpolar solvent such as acetone, acetonitrile, an alcohol, methylethylketone, methylisobutylketone, dimethylformamide, n-methylpyrrolidone, dimethylsulfoxide, hexamethylphosphoramide or combinations thereof.

In another embodiment, the solvent may be a solvent capable of forming an azeotrope with water, such as toluene or xylene. It has been surprisingly found that such solvents may be used to assist in the removal of both the water found in the compounds which form the reaction mixture (i.e. the polyhydric phenol compound comprising at least one furan or thiophene group, 4-nitrophthalonitrile and base) as well as the water formed during the reaction of the polyhydric phenol compound comprising at least one furan group or thiophene group and 4-nitrophthalonitrile. The phthalonitrile monomer may be purified by recrystallization from a mixture of solvent and water to enrich the monomer content of the resulting product.

According to another embodiment, the polyhydric phenol compound comprising at least one furan group or thiophene group and functionalized phthalonitrile monomer may be formed in the same reaction vessel to improve overall process time and efficiency. In such embodiments, in a first step, the polyhydric phenol comprising at least one furan group or thiophene group is formed in a reaction vessel as described above. In a second step, 4-nitrophthalonitrile is added to the polyhydric phenol comprising at least one furan group or thiophene group in the reaction vessel to form the functionalized phthalonitrile monomer. The base, catalyst and solvents which are used in the reactions in the first step and second step may be the same or different.

In some embodiments, the solvent is toluene or xylene.

The thermosetting composition according to claim 1, wherein the phthalonitrile monomer is a compound having the formula

Wherein each of R₁ to R₁₄ is independently selected from a hydrogen atom, a substituted or unsubstituted C₁-C₂₀ alkyl group, a substituted or unsubstituted C₂-C₂₀ alkenyl group, a substituted or unsubstituted C₂-C₂₀ alkynyl group, a substituted or unsubstituted C₆-C₂₀ aryl group, a substituted or unsubstituted C₂-C₂₀ heteroaryl group; and Z is selected from a direct bond, a substituted or unsubstituted C₁-C₂₀ alkyl group, a substituted or unsubstituted C₂-C₂₀ alkyl group with aryl or heteroaryl bridge, a substituted or unsubstituted C₂-C₂₀ alkenyl group, a substituted or unsubstituted C₂-C₂₀ alkynyl group, a substituted or unsubstituted C₆-C₂₀ aryl group, a substituted or unsubstituted C₂-C₂₀ heteroaryl group, O, S, S═O, O=S═O, C═O, C(═O)O, or C═CCl₂, or a polymer chain containing oxygen in each repeating unit of the polymer chain, including but not limited to polyether, polyethersulfone, or polyetherketone.

According to one embodiment, the polymerizable thermosetting composition comprises the one or more acetylene-bearing benzoxazine compound and phthalonitrile monomer in a weight ratio of the one or more acetylene-bearing benzoxazine compounds to phthalonitrile monomer of between about 1:1 to about 10:1, or from about 1.5:1 to about 10:1, or from about 2:1 to about 10:1.

The amount of the phthalonitrile monomer present in the polymerizable thermosetting composition may be in an amount of at least about 1% by weight, at least about 5% by weight, or at least about 10% by weight, or at least about 20% by weight, or at least about 30% by weight, or at least about 40% by weight, or at least about 50% by weight, or at least about 60% by weight, or at least about 70% by weight, or at least about 80% by weight, or at least about 90% by weight, or at least about 99% by weight, based on the total weight of the polymerizable thermosetting composition. In other embodiments, the amount of phthalonitrile monomer present in the polymerizable thermosetting composition may be in an amount of between about 1% by weight to about 99% by weight, or between about 5% by weight to about 90% by weight, or between about 10% by weight to about 80% by weight, or between about 20% by weight to about 70% by weight, or between about 30% by weight to about 60% by weight, based on the total weight of the polymerizable thermosetting composition.

The polymerizable thermosetting composition of the present disclosure may be cured by sufficient heating the polymerizable thermosetting composition so as to form a thermoset polymer. A curing agent may be used to speed up thermoset formation of the thermoset polymer. Thus, according to another embodiment, the polymerizable thermosetting composition further comprises a curing agent.

The curing agent which may be used includes, but is not limited to, aromatic amines, primary amines, secondary amines, diamines, polyamines, amine-substituted phosphazenes, phenols, strong acids, organic acids, strong organic acids, inorganic acids, metals, metallic salts, metallic salt hydrates, metallic compounds, halogen-containing aromatic amines, clays, and chemically modified clays. The use of clays or chemically modified clays may improve the mechanical and flammability properties of the thermoset. Typically, chemical modification of a clay involves replacing sodium ions with ammonium to form quaternary ammonium salts.

Specific curing agents include, but are not limited to, bis(4-(4-aminophenoxy)phenylsulfone (p-BAPS), bis(4-(3-aminophenoxy)phenylsulfone (m-BAPS), 1,4-bis(3-aminophenoxy)benzene (p-APB), 1,12-diaminododecane, diphenylamine, epoxy amine hardener, 1,6-hexanediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, p-toluene sulfonic acid, cuprous iodide, cuprous bromide, 1,3-bis(3-aminophenoxy)benzene (m-APB), 3,3′-dimethyl-4,4′-diaminodiphenylsulfone, 3,3′-diethoxy-4,4′-diaminodiphenylsulfone, 3,3′-dicarboxy-4,4′-diaminodiphenylsulfone, 3,3′-dihydroxy-4,4′-diaminodiphenylsulfone, 3,3′-disulfo-4,4′-diaminodiphenylsulfone, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-dimethyl-4,4′-diaminobenzophenone, 3,3′-dimethoxy-4,4′-diaminobenzophenone, 3,3′-dicarboxy-4,4′-diaminobenzophenone, 3,3′-dihydroxy-4,4′-diaminobenzophenone, 3,3′-disulfo-4,4′-diaminobenzophenone, 4,4′-diaminodiphenyl ethyl phosphine oxide, 4,4′-diaminodiphenyl phenyl phosphine oxide, bis(3-aminophenoxy-4′-phenyl)phenyl phosphine oxide, methylene dianiline, hexakis(4-aminophenoxy)cyclotriphosphazene, 3,3′-dichloro-4,4′-diaminodiphenylsulfone, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 2,2′-bis(4-aminophenyl)hexafluoropropane, bis [4-(4-aminophenoxy)phenyl]2,2′-hexafluoropropane, 1,1-bis(4-aminophenyl)-1-phenyl-2,2,2-trifluoroethane, 3,3′-dichloro-4,4′-diaminobenzophenone, 3,3′-dibromo-4,4′-diaminobenzophenone, aniline-2-sulfonic acid, 8-aniline-1-naphthalenesulfonic acid, benzene sulfonic acid, butylsulfonic acid, 10-camphorsulfonic acid, 2,5-diaminobenzenesulfonic acid, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid, 5-dimethylamino-1-naphthalene sulfonic acid, 4-hydroxy-3-nitroso-1-naphthalenesulfonic acid tetrahydrate, 8-hydroxyquinoline-5-sulfonic acid, methylsulfonic acid, phenylboric acid, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, 1,5-naphthalenedisulfonic acid, 2,6-naphthalenedisulfonic acid, 2.7-naphthalenedisulfonic acid, picrylsulfonic acid hydrate, 2-pyridineethane sulfonic acid, 4-pyridineethanesulfonic acid, 3-pyridine sulfonic acid, 2-pyridinylhydroxymethanesulfonic acid, sulfanilic acid, 2-sulfobenzoic acid hydrate, 5-sulfosalicylic acid hydrate, 2,4-xylenesulfonic acid, sulfonic acid containing dyes, organic phosphorus-containing acids, phenylphosphinic acid, diphenylphosphinic acid, propylphosphonic acid, 1-aminoethylphosphonic acid, 4-aminophenylphosphonic acid, butylphosphonic acid, t-butylphosphonic acid, 2-carboxyethylphosphonic acid, 2-chloroethylphosphonic acid, dimethylphosphonic acid, ethylphosphonic acid, methylenediphosphonic acid, methylphosphonic acid, phosphonoacetic acid, bis(hydroxymethyl) phosphonic acid, chloromethylphosphonic acid, di-n-butylphosphonic acid, dichloromethylphosphonic acid, diphenyldithiophosphonic acid, 1,2-ethylenediphosphonic acid, n-hystaderylphosphonic acid, hydroxymethylphosphonic acid, n-octadecylphosphonic acid, n-octylphosphonic acid, phenylphosphonic acid, propylenediphosphonic acid, n-tetradecylphosphonic acid, concentrated sulfuric acid, phenylphosphonic acid, copper, iron, zinc, nickel, chromium, molybdenum, vanadium, beryllium, silver, mercury, tin, lead, antimony, calcium, barium, manganese, magnesium, cobalt, palladium, platinum, cuprous bromide, cuprous cyanide, cuprous ferricyanide, zinc chloride, zinc bromide, zinc iodide, zinc cyanide, zinc ferrocyanide, zinc acetate, zinc sulfide, silver chloride, ferrous chloride ferric chloride, ferrous ferricyanide, ferrous chloroplatinate, ferrous fluoride, ferrous sulfate, cobaltous chloride, cobaltic sulfate, cobaltous cyanide, nickel chloride, nickel cyanide, nickel sulfate, nickel carbonate, stannic chloride, stannous chloride hydrate, stannous chloride dihydrate, aluminum nitrate hydrate, aluminum nitrate nonahydrate, triphenylphosphine oxide complex, montmorillonite, chemically modified montmorillonite, 4,4′-(1,3-phenylenedioxy)dianiline, 4,4′-(1,4-phenylenedioxy)dianiline, bis(4-(4-aminophenoxy)phenyl]sulfone, 4,4′-(4,4′-isopropylidenediphenyl-1,1′-diyldioxy)dianiline, 4,4′-(1,3-phenylenediisopropylidene)dianiline, 4,4′-(1,4-phenylenediisopropylidene)dianiline, 4,4′-(1,1′-biphenyl-4,4′-diyldioxy)dianiline, 4,4′-methylenedianiline, 4,4′-sulphonyldianiline, 4,4′-methylene-bis(2-methylaniline), 3,3′-methylenedianiline, 3,4′-methylenedianiline, 4,4′-oxydianiline, 4,4′-(isopropylidene)dianiline, 4,4′-(hexafluoroisopropylidene)dianiline, 4,4′-(hexafluoroisopropylidene)bis(p-phenyleneoxy)dianiline, 4,4′-diaminobenzophenone, the compounds

and mixtures thereof.

The curing agent may be present in the polymerizable thermosetting composition in an amount of at least about 0.5% by weight, or at least about 1% by weight, or at least about 2% by weight, or at least about 5% by weight, or at least about 10% by weight, at least about 15% by weight or even at least about 20% by weight, based on the total weight of the polymerizable thermosetting composition.

In other embodiments, the curing agent may be present in an amount of less than about 40% by weight, or less than about 35% by weight, or less than about 30% by weight, or less than about 25% by weight, based on the total weight of the polymerizable thermosetting composition. In still other embodiments, the curing agent may be present in an amount of between about 0.25% by weight to about 45% by weight, or between about 1% by weight to about 40% by weight, based on the total weight of the polymerizable thermosetting composition.

The polymerizable thermosetting composition may be prepared by mixing the acetylene-bearing benzoxazine compound with the phthalonitrile monomer at a temperature below the melting point (for example, but without limitation, at a temperature 35 to 40° C. or more below the melting point of the components) by using customary devices, such as a stirred vessel, stirring rod, ball mill, sample mixer, static mixer or ribbon blended to form the thermosetting composition.

The polymerizable thermosetting composition may then be cured to form the thermoset polymer. The expression “cured” as used herein, denotes the conversion of the above thermosetting composition into an insoluble and infusible crosslinked product, with simultaneous shaping to give a shaped article such as a molding, pressing or laminate or to give a two-dimensional structure such as a coating, enamel, or adhesive bond. Typical curing processes include ambient temperature cure to elevated temperature cure using thermal, radiation or any combination of energy sources.

Typical curing temperatures may range from between about 50° C. to about 500° C., such as between about 75° C. to about 375° C. or between about 80° C. to about 300° C. for a time sufficient to at least partially or substantially or fully cure the composition such as, for example, 3 to 20 hours, or from about 5 to 15 hours, or from about 6 to about 15 hours, or from about 7 to about 12 hours, or from about 8 to about 10 hours.

In addition, curing may occur in one or more curing stages. For example, the polymerizable thermosetting composition may be subjected to an initial cure at a temperature ranging from between about 50° C. to about 500° C., such as between about 75° C. to about 375° C. or between about 80° C. to about 300° C. for a time sufficient to at least partially cure the composition such as, for example, a time ranging from 3 to 10 hours, and then post-cured at a temperature below 300° C., or at or below 280° C. and even at or below 260° C. for a time sufficient to substantially or fully cure the composition such as, for example, a time ranging from 2 to 4 hours. The polymerizable thermosetting composition may have a viscosity at 75° C. of less than 3000 centipoise, or less than 1000 centipoise, or less than 500 centipoise, or less than 175 centipoises prior to being cured.

According to one embodiment, the polymerizable thermosetting composition of the present disclosure may further comprise additional monofunctional benzoxazine(s) or multifunctional benzoxazine(s) or combination thereof and any one or more of the curing agents and optional additives or a second phthalonitrile monomer to form another thermosetting composition. The additives may include, but not limited to, fillers, for example, carbon nanotubes, clays, carbon nanofibers, metal oxides, zinc oxides, diatomaceous earth, barium sulfate, talc, silica, calcium carbonate, calcium fluoride and combinations thereof, colorants, anti-oxidant stabilizers, thermal degradation stabilizers, light stabilizers, flow agents, bodying agents, flatting agents, binders, blowing agents, fungicides, bactericides, surfactants, plasticizers, rubber tougheners, and other additives known to those skilled in the art. These additives, if present, are added in an amount effective for their intended purpose.

As described above, the polymerizable thermosetting composition may be prepared by mixing in any order at least one acetylene-bearing benzoxazine compound and one phthalonitrile monomer, other monofunctional or multifunctional benzoxazines, or an second phthalonitrile monomer and optional curing agent and additives using customary devices, such as a stirred vessel, stirring rod, ball mill, sample mixer, static mixer or ribbon blended to form the thermosetting composition. The thermosetting composition may then be cured as described above to form the thermoset polymer.

According to one embodiment, the additional benzoxazine may be a monofunctional benzoxazine. The monofunctional benzoxazine compound is a compound obtained from the reaction of a monophenolic compound, an aldehyde, such as formaldehyde, and a primary amine.

The monophenolic compound may be, but not limited to, phenol cresol, 2-bromo-4-methylphenol,2-allylphenol, 1,4-aminophenol and the like. In one particular embodiment, the phenol-type is a phenol.

The aldehyde compound may be, but is not limited to, formaldehyde, paraformaldehyde, polyoxymethylene or a compound having the formula R_(a)CHO where R_(a) is a C₁-C₁₂ aliphatic group. In one particular embodiment, the aldehyde compound is paraformaldehyde.

The primary amine may be, but is not limited to, those primary amines having at least one carbon to carbon triple bond group described above, as well as aniline, o-, m- and p-phenylene diamine, benzidine, 4,4′-diaminodiphenyl methane, cyclohexylamine, 1,4-diaminocyclohydexyl, butylamine, methylamine, hexylamine, allylamine, furfuryl amine, ethylenediamine, propylenediamine and diaminodiphenyl sulfone. In one particular embodiment, the primary amine is furfuryl amine.

According to another embodiment, the additional benzoxazine may be a multifunctional benzoxazine. The multifunctional benzoxazine is a compound having the formula

wherein b is an integer ranging from 2 to 4; each R is independently hydrogen, a substituted or unsubstituted C₁-C₂₀ alkyl group, a substituted or unsubstituted C₂-C₂₀ alkenyl group, a substituted or unsubstituted C₆-C₂₀ aryl group, a substituted or unsubstituted C₂-C₂₀ heteroaryl group, a substituted or unsubstituted C₄-C₂₀ carbocyclic group, a substituted or unsubstituted C₂-C₂₀ heterocyclic group, or a C₃-C₈ cycloalkyl group; each R₁ is independently hydrogen, a C₁-C₂₀ alkyl group, a C₂-C₂₀ alkenyl group, or a C₆-C₂₀ aryl group; and when b is 2, Z is a direct bond, a substituted or unsubstituted C₁-C₂₀ alkyl group, a substituted or unsubstituted C₆-C₂₀ aryl group, a substituted or unsubstituted C₂-C₂₀ heteroaryl group, O, S, S═O, O=S=O or C═O, and when b is 3 or 4, Z is a substituted or unsubstituted C₁-C₂₀ alkyl group, a substituted or unsubstituted C₆-C₂₀ aryl group, a substituted or unsubstituted C₂-C₂₀ heteroaryl group.

Substituents include, but are not limited to, hydroxy, C₁-C₂₀ alkyl, C₂-C₁₀ alkoxy, mercapto, C₃-C₈ cycloalkyl, C₆-C₁₄ heterocyclic, C₆-C₁₄ aryl, C₆-C₁₄ heteroaryl, halogen, cyano, nitro, nitrone, amino, amido, acyl, oxyacyl, carboxyl, carbamate, sulfonyl, sulfonamide and sulfuryl.

According to one embodiment, the multifunctional benzoxazine compound above is a compound obtained from the reaction of a multifunctional phenolic compound, an aldehyde, such as formaldehyde, and a primary amine.

The multifunctional phenolic compound may be, but is not limited to, resorcinol, bisphenol A, bisphenol F, bisphenol E, bisphenol S, 1,2,2,2-tetraphenolethane, thiodiphenol, phenolphthalein, dicyclopentadienyidiphenol, 1,8-hydroxyanthraquinone, 1,6-dihydroxynaphthalene, 2-2′-dihydroxyazobenzene and 1,3,5-trihydroxybenzene. In one particular embodiment, the multifunctional phenolic compound is 4′4-diphenol or 4,4-thiodiphenol.

The primary amine may be, but is not limited to, those primary amines having at least one carbon to carbon triple bond group described above, as well as aniline, o-, m- and p-phenylene diamine, benzidine, 4,4′-diaminodiphenyl methane, cyclohexylamine, 1,4-diaminocyclohydexyl, butylamine, methylamine, hexylamine, allylamine, furfurylamine, ethylenediamine, propylenediamine and diaminodiphenyl sulfone. In one particular embodiment, the primary amine is aniline and furfurylamine.

In still another embodiment, there is provided a thermoset polymer obtained by contacting any suitable substrate with any one of the polymerizable thermosetting compositions described above and subjecting the substrate/polymerizable thermosetting composition to thermal, radiation or a combination of energy sources to cure the substrate/polymerizable thermosetting composition. In one embodiment, the polymerizable thermosetting compositions of the present disclosure may be used to bond one or more substrates together by contacting one or more surfaces of like or dissimilar substrates that are to be bonded with the polymerizable thermosetting composition under conditions sufficient to cure the polymerizable thermosetting composition.

In an alternative embodiment, by curing the polymerizable thermosetting compositions of the present disclosure, a composite article may be obtained by techniques well known in the industry, for example, pultrusion, infusion, molding, encapsulating or coating. Thus, the polymerizable thermosetting composition of the present disclosure may be used in methods for manufacturing composite articles, such as castings, prepregs, bonding sheets, laminates and metal-foil clad laminates.

The properties of the composite articles can be tailored for certain applications by the addition of reinforcement fibers. Examples of reinforcement fibers include glass, quartz, carbon, alumina, ceramic, metallic, aramid, natural fibers (e.g. flax, jute, sisal, hemp), paper, acrylic and polyethylene fibers and mixtures thereof. The reinforcement fibers may be in any of various modes, for example, as a strand or roving formed by paralleling continuous fibers or discontinuous fibers (short fibers) in one direction, cloth such as woven fabric or mat, braids, unidirectional, bi-directional, random, pseudo-isotropic or three-dimensionally dispersed mat-like material, heterogeneous lattice or mesh material, and three-dimensional material such as triaxially woven fabric.

Thus, in another embodiment, there is provided a process for producing a composite article including the steps of: contacting a layer of reinforcement fibers with the polymerizable thermosetting composition to coat and/or impregnate the reinforcement fibers; and curing the coated and/or impregnated reinforcement fibers to produce the composite article.

Coating and/or impregnation may be affected by either a wet method or hot melt method. In the wet method, the thermosetting composition is first dissolved in a solvent to lower viscosity, after which coating and/or impregnation of the reinforcement fibers is effected and the solvent evaporated off using an oven or the like.

In the hot melt method, coating and/or impregnation may be effected by directly coating and/or impregnating the reinforcement fibers with the polymerizable thermosetting composition, which may have been heated to reduce its viscosity, or alternatively, a coated film of the polymerizable thermosetting composition may first be produced on release paper or the like, and the film placed on one or both sides of the reinforcement fibers and heat and pressure applied to effect coating and/or impregnation.

According to another aspect, there is provided a process for producing a composite article in a RTM system. The process includes the steps of: a) introducing a fiber preform comprising reinforcement fibers into a mold; b) injecting the polymerizable thermosetting composition into the mold, c) allowing the polymerizable thermosetting composition to impregnate the fiber preform; and d) heating the resin impregnated preform for a period of time to produce an at least partially cured solid article; and optionally e) subjecting the partially cured solid article to additional heat.

In still another embodiment, there is provided a process for forming a composite article in a VaRTM system. The process includes the steps of a) introducing a fiber preform comprising reinforcement fibers into a mold; b) injecting the polymerizable thermosetting composition into the mold; c) reducing the pressure within the mold; d) maintaining the mold at about the reduced pressure; e) allowing the polymerizable thermosetting composition to impregnate the fiber preform; f) heating the resin impregnated preform to produce an at least partially cured solid article; and optionally g) subjecting the at least partially cured solid article to additional heat.

Besides RTM and VaRTM systems, the polymerizable thermosetting composition may be used in other methods and systems for producing composite articles including hot-pressing of prepregs, sheet molding compound, molding, casting, pultrusion and filament winding.

In another embodiment, the polymerizable thermosetting composition, upon curing, provides a thermoset polymer with excellent well-balanced physical, mechanical and thermal properties. The properties of the polymerizable thermoset polymer that are well-balanced in accordance with the present disclosure may include at least two of: a glass transition temperature (T_(g)) of greater than about 250° C., or greater than about 270° C., or greater than about 290° C.; a storage modulus greater than 3500 MPa, or greater than 3750 MPa, or greater than 4000 MPa; and, a char yield of at least 60%, or at least 65%, or at least 70% at 800° C. under nitrogen.

The polymerizable thermosetting composition and composite articles of the present disclosure may be used in various applications, for example, in aerospace applications, where they may be employed as aircraft primary structural materials (main wings, tail wing, floor beam, etc.), secondary structural materials (flap, aileron, cowl, fairing, interior trim, etc.), rocket motor cases, structural materials for artificial satellites or other moving bodies such as cars, boats and railway carriages, in drive shafts, fuel cells, plate springs, wind turbine blades, pressure vessels, fly-wheels, papermaking rollers and civil engineering and building materials (roofing materials, cables, reinforcing bars, retrofitting materials).

EXAMPLES

Chemicals analysis methods such as NMR, FTIR, LC-MS, GPC, and HPLC were run by analytical service group inside Huntsman Corporation; DSC, DMA and TGA were run on TA instruments, such as DSCQ2000, DSC 2500, DMA 800, TGA 5000, SDT650, viscosities were run on Brookfield CAP+2000.

Example 1: Synthesis and Homo-Polymerization of phenol 3-aminophenyl acetylene benzoxazine (Phenol-APA)

To a 3000 mL, 4-necked round bottom flask fitted with a thermometer, a condenser, and a nitrogen inlet were added phenol (376 g, 4.0 mol), paraformaldehyde (263.8 g, 8.8 mol), and toluene (1200 ml). The mixture was heated to 60° C., and to the stirring mixture was then added 3-aminophenyl acetylene (468.1 g, 4.0 mol). The resulting mixture was then heated to 80° C. for an hour, and then further heated to 100° C. to remove most of the water by azeotropic process. The reaction mixture was further heated to 110° C. until the reaction completed, forming the product. After filtration, the product was washed with 3 N sodium hydroxide and then water, and dried. Then, any remaining toluene was removed under vacuum, and the product was further dried in vacuo for 3 hours at 110° C. to yield 835 g (89%) of the product as a brown solid upon cooling down. The material was measured to have a melting range between 53-55° C. by DSC scan at 10° C./min. The major component monomer is about 73%, dimers about 20%, and trimers about 7% by GPC analysis and the monomer has the spectrum as follows: ¹H NMR (400 MHz; ppm, in CDCl₃): 7.20 (dd, 1H), 7.15 (d, 1H), 7.00-7.10 (m, 3H), 6.95 (d, 1H), 6.86 (dd, 1H), 6.81 (d, 1H), 5.29 (s, 2H), 4.56 (s, 2H), 3.02 (s, 1H); ¹³C NMR (400 MHz; ppm, in CDCl₃): 154.2, 148.2, 129.2, 127.9, 126.7, 125.0, 122.9, 121.4, 120.9, 120.56, 118.6, 117.0, 83.8, 78.8, 77.1, 50.2. LCMS: 236.1074 (M+H⁺, calc. 236.1075).

To an aluminum pan was charged with 14 grams of phenol 3-aminophenyl acetylene benzoxazine (Phenol-APA). The aluminum pan was then put into an 80° C. vacuum oven to be melted and degassed for 1 hour. After degassing, the material was staged cured at 120° C. for 2 hours, 150° C. for 2 hours, 180° C. for 2 hours, and 200° C. for 2 hours. The DSC of the fresh made sample, and the DMA, TGA of one half of the cured product were determined. The other half of the cured product was further post cured at 250° C. for 3 hours and the DMA and TGA of this cured product were also determined. The results are shown below in Tables 1 and 2.

Example 2. Synthesis and Homo-Polymerization of 2-allylphenol 3-aminophenyl acetylene benzoxazine (AllylPh-APA)

To a 1000 mL, 4-necked round bottom flask fitted with a thermometer, a condenser, and a nitrogen inlet were added 2-allylphenol (134 g, 1.0 mol), paraformaldehyde (62.9 g, 2.1 mol), and toluene (205 ml) and butanol (34 ml). Heat the mixture to 70° C., and to the stirring mixture was then added 3-aminophenyl acetylene (117 g, 1.0 mol). The resulting mixture was then heat to 100° C. to remove most of water by azeotropic process. The reaction mixture further heated to 110° C. for completeness. After filtration, washed with 3 N sodium hydroxide and then water, and dried. After solvent removed under vacuum, the product was further dried in vacuo for 3 hours in 100° C. to yield 250 g (90%) the product as a brownish liquid. The major component monomer is about 76%, dimers about 12%, trimer about 5% by GPC analysis. The major component has ¹H NMR (ppm, CDCl₃): 7.10-7.30 (m, 4H), 6.90-7.00 (m, 2H), 6.81 (dd, 1H), 5.88-5.96 (m, 1H), 5.43 (s, 2H), 4.95-5.05 (m, 2H), 4.62 (s, 2H), 4.08 (s, 1H), 3.24 (d, 2H); ¹³C NMR (ppm, CDCl₃): 151.7, 147.9, 136.5, 129.6, 128.1, 127.9, 127.1, 125.3, 123.8, 122.4, 120.7, 120.1, 120.0, 118.1, 115.6, 83.8, 80.1, 78.2, 49.4, 31.3; LC-MS: 276.1388 (M+H⁺; calc. 276.1388).

To an aluminum pan was charged with 14 grams of 2-allylphenol 3-aminophenyl acetylene benzoxazine (AllPh-APA). The aluminum pan was then put into an 80° C. vacuum oven to be melted and degassed for 1 hour. After degassing, the material was staged cured at 120° C. for 2 hours, 150° C. for 2 hours, 180° C. for 2 hours, and 200° C. for 2 hours. The DSC of the fresh made sample, and the DMA, TGA of one half of the cured product were determined. The other half of the cured product was further post cured at 250° C. for 3 hours and the DMA and TGA of this cured product were also determined. The results are shown below in Table 1 and 2.

Example 3: Synthesis and Homo-Polymerization of 2,2′,6′6′-tetramethylbisphenol F phthalonitrile (TMBF-PN)

To a 1000 mL, 4-necked round bottom flask fitted with a thermometer, a condenser, and a nitrogen inlet were added 2,2′6,6′-tetramethyl bisphenol F (100 g, 0.39 mol), 4-nitrophthalonitrile (135.1 g, 0.78 mol), and DMF (350 ml). Then K₂CO₃ (148.6 g, 1.05 mol), was added. The resulting mixture was heated to 80-90° C. for 2-3 hours. The mixture was cooled to ambient temperature and poured into diluted HCl to precipitate. Precipitation were collected by filtration, washed with water until neutral then washed with methanol. The solid was vacuum dried to yield 194 g, (98%) crude product as tan solid with purity above 95% by HPLC analysis at 254 nm. Further recrystallization from acetonitrile yield the product as off-white powder, with the purity above 97%. m.p by DSC scan up to 400° C. at 10° C./min 191-193° C. ¹H NMR (ppm, CDCl₃): 7.733 (d, 2H), 7.14-7.17 (m, 4H), 7.01 (s, 4H), 3.91 (s, 2H), 2.21 (s, 2H), 1.99 (s, 12H); ¹³C NMR (ppm, CDCl₃): 161.164 (2C), 147.872 (2C), 139.112 (2C), 135.652 (2C), 130.582 (4C), 130.010 (4C), 119.823 (2C), 119.660 (2C), 117.744 (2C), 115.498 (2C), 115.130 (2C), 108.246 (2C), 40.690 (1C), 16.192 (4C); FTIR (cm-1) 3105.88, 3077.27, 3042.23, 2949.33, 2916.23, 2860.75, 2231.82, 1592.23, 1567.61, 1479.62, 1444.10, 1420.06, 1411.25, 1382.71, 1372.87, 1329.94, 1307.01, 1277.14, 1244.61, 1191.46, 1162.48, 1134.01, 1085.95, 1020.57, 980.57, 972.99, 961.75, 949.15, 904.55, 895.84, 885.14, 868.92, 848.79, 840.06, 808.47, 765.01, 757.67, 727.54, 720.58, 688.45, 662.06; LC-MS: C33H24N4O2 (MW: 508, 98.16%).

To an aluminum pan was charged with 14 grams of the phthalonitrile monomer. The aluminum pan was then put into a 200° C. oven to melt the material. After that, the material was staged cured at 260° C. for 6 hours at 300° C. for 3 hours and 350° C. for 4 hours. The DMA and TGA of this cured product were also determined. The results are shown below in Table 1 and 2.

Example 4. Synthesis and Homopolymerization of furanyl-2,2′-6,6′-tetramethylbisphenol F phthalonitrile (FTMBF-PN)

Step 1: To a 500 ml 4-neck round bottom flask equipped with a mechanical stirrer and a reflux condenser was charged 61.08 grams of 2,6-xylenol and 32.04 grams of methanol. 2 grams of sodium hydroxide was then added and dissolved with stirring. The resulting mixture was heated to reflux and 24.0 grams of furfural was added dropwise under reflux over a 2 hour time period. The mixture was then refluxed for an additional 15 hours and monitored by HPLC for complete conversion after which the mixture was neutralized with 35 grams of 20% aqueous sodium dihydrogenphosphate. Precipitated crystals were collected by filtration, washed with a 1:1 methanol/water solution and dried in a vacuum drying oven. 72.6 grams of tetramethyl bisphenol furan (90.8%) were produced. The product was found to be very pure on HPLC (99.7%).

Step 2: To a 1000 mL 4-necked round bottom flask fitted with a thermometer, a Dean-Stark trap with condenser, and a nitrogen inlet, were added furanyl-tetramethyl bisphenol from step 1 (32.2 grams, 0.1 mole), powdered K₂CO₃ (33.2 grams, 0.24 mole), toluene (100 mL), and N,N-dimethylformamide (DMF) (146.1 grams). The resulting mixture was degassed with nitrogen, and the mixture was heated to reflux at 140° C. for 10-12 hours. The toluene was then removed by distillation and the reaction mixture was cooled to 30° C. 4-nitrophthalonitrile (35.3 grams, 0.204 mole) was then added in one portion and the reaction mixture was heated at 80° C. and monitored by HPLC for complete conversion. The mixture was then cooled to ambient temperature and poured into cold deionized water resulting in the formation of a solid. Precipitated crystals were collected by filtration, washed with cold deionized water until neutral and then washed with 1:1 methanol/water solution. The dark yellow solid that was obtained was vacuum dried to yield 54.5 grams, (95%) of the title product. The melting point the product found to be 219.6° C. by DSC scan at 10° C./min. ¹H NMR (ppm, CDCl₃): 7.733 (d, 2H), 7.437 (dd, 1H), 7.13-7.17 (m, 4H), 7.00-7.03 (s, 4H), 6.374 (dd, 1H), 6.036 (d, 1H), 5.39 (s, 1H), 2.09 (s, 12H); ¹³C NMR (ppm, CDCl₃): 160.981 (2C), 155.809 (1C), 148.253 (2C), 142.181 (1C), 139.815 (2C), 135.694 (2C), 130.663 (4C), 129.794 (4C), 119.817 (2C), 119.714 (2C), 117.689 (2C), 115.499 (2C), 115.123 (2C), 110.266 (1C), 108.500 (1C), 108.280 (2C), 49.745 (1C), 16.296 (4C); FTIR (cm-1) 3111.2, 3075.5, 3043.7, 2963.5, 2921.2, 2862.4, 2231.2, 1673.8, 1582.7, 1564.0, 1478.0, 1421.8, 1310.4, 1276.7, 1244.7, 1182.0, 1163.2, 1133.4, 1087.2.80, 1011.5, 950.0, 880.4, 835.6, 781.3, 734.8.

To an aluminum pan was charged with 14 grams of the phthalonitrile monomer. The aluminum pan was then put into a 220° C. oven to melt the material. After that, the material was stage cured at 260° C. for 6 hours, at 300° C. for 3 hours and 350° C. for 4 hours. The DMA and TGA of this cured product were also determined. The results are shown below in Table 1 and 2.

Example 5: Synthesis and Homo-Polymerization of bisphenol A phthalonitrile (BisA-PN)

To a 1000 mL, 4-necked round bottom flask fitted with a thermometer, a condenser, and a nitrogen inlet were added bisphenol A (80 g, 0.35 mol), 4-nitrophthalonitrile (121.3 g, 0.7 mol), and DMF (300 ml). Then Pulverized K₂CO₃ (133.5 g, 1.05 mol), was added. The resulting mixture was heated to 80-90° C. for 2-3 hours. The mixture was cooled to ambient temperature and poured into diluted HCl resulting in the formation of a solid. Precipitation were collected by filtration, washed with water until neutral then washed with methanol. The solid was vacuum dried to yield 166 g, (99%) crude product as green powder with purity about 93% by HPLC analysis at 280 nm. Further recrystallization from acetonitrile yield the product as green crystals (82.5% yield), with the purity above 97%. m.p by DSC scan at 10° C./min 198° C. ¹H NMR (ppm, CDCl₃): 7.733 (d, 2H), 7.33-7.36 (m, 4H), 7.27-7.29 (m, 4H), 7.00-7.03 (m, 4H), 3.91 (s, 2H), 2.21 (s, 2H), 1.759 (s, 6H); ¹³C NMR (ppm, CDCl₃): 161.818 (2C), 151.584 (2C), 148.304 (2C), 135.419 (2C), 128.979 (4C), 121.619 (2C), 121.364 (2C), 120.223 (4C), 117.597 (2C), 115.401 (2C), 115.043 (2C), 108.796 (2C), 42.707 (1C), 30.938 (2C); FTIR (cm-1) 3074.13, 3050.53, 2973.19, 2935.48, 1876.84, 2233.15, 1915.12, 1669.92, 1589.05, 1560.79, 1502.11, 1485.78, 1422.65, 1407.54, 1388.51, 1366.70, 1305.39, 1288.35, 1251.36, 1209.84, 1176.79, 1163.28, 1112.99, 1103.00, 1081.80, 1016.02, 952.72, 922.78, 903.99, 887.50, 854.97, 854.07, 825.63, 777.60, 745.25, 717.42, 697.67, 671.03; LC-MS C31H20N4O2 (Exact mass 480, 97.79%).

To an aluminum pan was charged with 14 grams of the phthalonitrile monomer. The aluminum pan was then put into a 220° C. oven to melt the material. After that, the material was staged cured at 260° C. for 6 hours, at 300° C. for 3 hours and 350° C. for 4 hours. The DMA and TGA of this cured product were also determined. The results are shown below in Table 1 and 2.

Example 6: Synthesis and Homo-Polymerization of bisphenol C phthalonitrile (BisC-PN)

To a 1000 mL, 4-necked round bottom flask fitted with a thermometer, a condenser, and a nitrogen inlet were added bisphenol C (76.9 g, 0.27 mol), 4-nitrophthalonitrile (94.7 g, 0.55 mol), and DMF (250 ml). Then Pulverized K₂CO₃ (104.2 g, 0.82 mol), was added. The resulting mixture was heated to 80-90° C. for 2-3 hours. The mixture was cooled to ambient temperature and poured into diluted HCl resulting in the formation of a solid. Precipitation were collected by filtration, washed with water until neutral then washed with methanol. The solid was vacuum dried to yield 142 g, (99%) crude product as yellow solid with purity above 97% by HPLC analysis at 280 nm. Further recrystallization from acetonitrile yield the product as light tan powder (87.5% yield), with the purity above 99%. m.p by DSC scan at 10° C./min 198° C. ¹H NMR (ppm in DMSO) 8.126 (d, 2H), 7.860 (d, 2H), 7.43-7.50 (m, 6H), 7.21-7.25 (m, 4H); ¹³C NMR (ppm in DMSO) 160.191 (2C), 153.850 (2C), 139.172 (1C), 136 299 (2C), 135.697 (2C), 131.119 (4C), 123.343 (2C), 122.636 (2C), 119.849 (4C), 119.039 (1C), 116.734 (2C), 115.740 (2C), 115.254 (2C), 108.726 (2C), 41.246 (2C), 29.284 (4C); FTIR (cm-1) 3066.78, 3041.52, 2228.20, 1606.69, 1590.35, 1560.94, 1499.85, 1483.70, 1416.10, 1306.05, 1295.19, 1279.97, 1246.74, 1210.05, 1169.39, 1161.41, 1154.56, 1102.68, 1089.03, 1016.18, 978.14, 967.00, 952.81, 941.27, 916.08, 878.81, 869.26, 857.37, 844.35, 829.40, 819.90, 781.88, 744.44, 721.67, 703.65, 692.30, 681.79; LC-MS: C32H14Cl2N4O2, (Exact mass 532, 99.31%);

To an aluminum pan was charged with 14 grams of the phthalonitrile monomer. The aluminum pan was then put into a 220° C. oven to melt the material. After that, the material was staged cured at 260° C. for 6 hours, at 300° C. for 3 hours and 350° C. for 4 hours. The DMA and TGA of this cured product were also determined. The results are shown below in Table 1 and 2.

Example 7: Synthesis and Homo-Polymerization of bisphenol M phthalonitrile (BisM-PN)

To a 1000 mL, 4-necked round bottom flask fitted with a thermometer, a condenser, and a nitrogen inlet were added bisphenol M (120 g, 0.35 mol), 4-nitrophthalonitrile (119.9 g, 0.69 mol), and DMF (420 ml). Then pulverized K₂CO₃ (105.6 g, 0.83 mol), was added. The resulting mixture was heated to 80-90° C. for 2-3 h. The mixture was cooled to ambient temperature and poured into diluted HCl resulting in the formation of a solid. Precipitation were collected by filtration, washed with water until neutral then washed with methanol. The solid was vacuum dried to yield 205 g, (98%) crude product as dark tan solid with purity above 96% by HPLC analysis at 280 nm. Further recrystallization from acetonitrile yield the product as light tan powder (yield 78%), with the purity above 98%. m.p by DSC scan at 10° C./min 135.12° C. ¹H NMR (ppm in DMSO) 8.066 (d, 2H), 7.67 (d, 2H), 7.20-7.35 (m, 7H), 7.05-7.11 (m, 7H), 1.638 (s, 12H); ¹³C NMR (ppm in DMSO) 159.988 (2C), 150.192 (2C), 148.376 (2C), 146.734 (2C), 135.092 (2C), 127.485 (4C), 126.664 (1C), 122.913 (1C), 122.631 (2C), 121.147 (2C), 120.525 (2C), 118.561 (4C), 115.516 (2C), 114.665 (2C), 114.170 (2C), 106.860 (2C), 41.246 (2C), 29.284 (4C); FTIR (cm-1) 3108.42, 3074.20, 3040.59, 2967.77, 2932.21, 2870.46, 2234.51, 1799.58, 1591.81, 1563.28, 1503.29, 1488.99, 1460.22, 1449.76, 1417.43, 1404.26, 1386.74, 1364.16, 1310.41, 1285.60, 1257.00, 1248.90, 1212.76, 1174.34, 1164.33, 1122.44, 1102.23, 1085.13, 1075.58, 967.63, 954.21, 931.93, 900.74, 889.01, 853.17, 833.42, 799.02, 767.81, 755.62, 709.86, 669.62; LC-MS: C40H30N4O2 (Exact mass 598, 98.69%).

To an aluminum pan was charged with 14 grams of the phthalonitrile monomer. The aluminum pan was then put into a 160° C. oven to melt the material. After that, the material was staged cured at 260° C. for 6 hours, at 300° C. for 3 hours and 350° C. for 4 hours. The DMA and TGA of this cured product were also determined. The results are shown below in Table 1 and 2.

Example 8: Synthesis and Homo-Polymerization of bisphenol P phthalonitrile (BisP-PN)

To a 1000 mL, 4-necked round bottom flask fitted with a thermometer, a condenser, and a nitrogen inlet were added bisphenol P (120 g, 0.35 mol), 4-nitrophthalonitrile (119.9 g, 0.69 mol), and DMF (420 ml). Then Pulverized K₂CO₃ (105.6 g, 0.83 mol), was added. The resulting mixture was heated to 80-90° C. for 2-3 h. The mixture was cooled to ambient temperature and poured into diluted HCl resulting in the formation of a solid. Precipitation were collected by filtration, washed with water until neutral then washed with methanol. The solid was vacuum dried to yield 203 g (97%) crude product as green solid with purity above 90% by HPLC analysis at 280 nm. Further recrystallization from acetonitrile yield the product as tan powder (77% yield), with the purity about 96%. m.p by DSC scan at 10° C./min 202° C. ¹H NMR (ppm in CDCl₃) 7.72 (dd, 2H), 7.25-7.35 (m, 8H), 7.18 (s, 4H), 6.97 (d, 4H), 1.711 (s, 12H); ¹³C NMR (ppm in CDCl₃) 161.887 (2C), 151.282 (2C), 148.938 (2C), 147.390 (2C), 135.388 (2C), 129.002 (4C), 126.422 (4C), 121.528 (1C), 121.355 (1C), 119.960 (4C), 117.495 (2C), 115,437 (2C), 115.054 (2C), 108.607 (2C), 42.424 (2C), 30.837 (4C); FTIR (cm-1) 3084.57, 3066.92, 3042.90, 2963.99, 2373.24, 2233.54, 1915.82, 1670.85, 1590.88, 1565.28, 1502.28, 1483.15, 1425.21, 1405.91, 1393.05, 1362.04, 1303.82, 1290.16, 1280.14, 1247.91, 1211.87, 1175.44, 1156.94, 1122.50, 1087.47, 1082.14, 1014.40, 954.30, 890.11, 879.46, 855.92, 831.87, 767.27, 719.31, 699.82; LC-MS: C₄₀H₃₀N₄O₂ (Exact Mass: 598, 96.34%).

To an aluminum pan was charged with 14 grams of the phthalonitrile monomer. The aluminum pan was then put into a 200° C. oven to melt the material. After that, the material was staged cured at 260° C. for 6 hours, at 300° C. for 3 hours and 350° C. for 4 hours. The DMA and TGA of this cured product were also determined. The results are shown below in Table 1 and 2.

Example 9: Synthesis and Homo-Polymerization of phenol furfurylamine benzoxazine (Phenol-FA)

To a 2000 mL, 4-necked round bottom flask fitted with a thermometer, a condenser, and a nitrogen inlet were added phenol (300 g, 3.19 mol), paraformaldehyde (200.9 g, 6.69 mol), and toluene (880 ml). Heat the mixture to 60° C., and to the stirring mixture was then added Furfuryl amine (309.4.1 g, 3.19 mol). The resulting mixture was then heat to 80° C. for an hour, then to 100° C. to remove most of water by azeotropic process. The reaction mixture further heated to 110° C. for completeness. After filtration, washed with 3 N sodium hydroxide and then water, and dried. After toluene removed under vacuum, the product was further dried in vacuo for 3 hours in 100° C. to yield 646 g (94.5%) the product as a brown solid upon cooling down. The material has a melting range between 54-56° C. by DSC scan at 10° C./min and used directly in the composition without further purification. The major component monomer is about 73%, dimer is about 11% by GPC analysis and the monomer has the spectrum as follows: ¹H NMR (ppm, CDCl₃): 7.40 (d, 1H), 7.11 (dd, 1H), 6.93 (d, 1H), 6.87 (dd, 1H), 6.80 (d, 1H), 6.32 (d, 1H), 6.23 (d, 1H), 4.87 (s, 2H), 4.00 (s, 2H), 3.91 (s, 2H); ¹³C NMR (ppm, CDCl₃): 154.0, 151.7, 142.6, 127.8, 127.6, 120.8, 119.7, 116.5, 110.2, 108.9, 81.8, 49.6, 48.2. LC-MS: 236.1074 (M+H⁺, calc. 236.1075).

To an aluminum pan was charged with 14 grams of phenol furfuryl amine benzoxazine. The aluminum pan was then put into an 80° C. vacuum oven to be melted and degassed for 1 hour. After degassing, the material was staged cured at 120° C. for 2 hours, 150° C. for 2 hours, 180° C. for 2 hours, and 200° C. for 2 hours. The DSC of the fresh made sample, and the DMA, TGA of one half of the cured product were determined. The other half of the cured product was further post cured at 250° C. for 3 hours and the DMA and TGA of this cured product were also determined. The results are shown below in Table 1 and 2.

Example 10: Synthesis and Homo-Polymerization of 4,4′-thiodiphenol aniline benzoxazine (TDP-AN)

To a 2000 mL, 4-necked round bottom flask fitted with a thermometer, a condenser, and a nitrogen inlet were added 4,4′-thiodiphenol (66 g, 0.3 mol), paraformaldehyde (38.1 g, 1.27 mol), and toluene (300 mL). Then aniline (56.3 g, 0.6 mol) was added dropwise. The reaction mixture was then heated to 80° C. for 1 hour, further heated to 100 o and water was collected by azeotropic distillation. After done in 14 hours, the reaction mixture was cooling down, toluene was removed by rotary evaporation, the residue was further dried in an 80° C. vacuum oven overnight to yield 420 g (94.5%) the product as sticky solid. The material has a melting point ° C. by DSC scan at 10° C./min and used directly in the composition without further purification. The monomer is about 52%, dimer is about 18%, trimers about 11%, tetramers is about 6% by GPC analysis and the monomer has the spectrum: ¹H NMR (ppm, CDCl₃): 7.0-7.3 (m, 12H), 6.856 (dd, 2H), 6.72 (d, 2H), 5.432 (s, 4H), 4.610 (s, 4H); ¹³C NMR (ppm, CDCl₃): 153.552 (2C), 147.518 (2C), 130.746 (1C), 129.996 (1C), 129.046 (6C), 128.823 (1C), 128.116 (1C), 126.097 (1C), 122.408 (1C), 120.562 (2C), 117.304 (6C), 78.818 (2C), 43.629 (2C). LCMS: 453.1694 (M+H+, calc. 453.1637).

To an aluminum pan was charged with 14 grams of the benzoxazine. The aluminum pan was then put into an 80° C. vacuum oven to be melted and degassed for 1 hour. After degassing, the material was staged cured at 120° C. for 2 hours, 150° C. for 2 hours, 180° C. for 2 hours, and 200° C. for 2 hours. The DSC of the fresh made sample, and the DMA, TGA of one half of the cured product were determined. The other half of the cured product was further post cured at 250° C. for 3 hours and the DMA and TGA of this cured product were also determined. The results are shown below in Table 1 and 2.

Example 11: Synthesis and Homo-Polymerization of 4,4′-biphenol furfuryl amine benzoxazine (BP-FA)

To a 2000 mL, 4-necked round bottom flask fitted with a thermometer, a condenser, and a nitrogen inlet were added diphenol (200 g, 1.07 mol), paraformaldehyde (135.4 g, 4.51 mol), furfuryl amine (208.5 g, 2.15 mol), and (720 ml). Heat the mixture to 100° C. until complete. After cooling down, white precipitate was collected by filtration, and washed with additional dioxanes and ethanol. The product was further dried in an 80° C. vacuum oven overnight to yield 420 g (94.5%) the product as an off-white solid. The material has a melting point about ° C. by DSC scan at 10° C./min and used directly in the composition without further purification. The major component is about 88% by GPC analysis and has the spectrum as follows: ¹H NMR (ppm, CDCl₃): 7.21 (d, 2H), 7.30 (dd, 2H), 7.09 (dd, 2H), 6,83 (d, 2H), 6.34 (m, 2H), 6.23 (m, 2H), 4.90 (s, 2H), 4.04 (s, 2H), 3.96 (s, 2H); ¹³C NMR (ppm, CDCl₃): 153.2 (2C), 151.6 (2C), 142.6 (2C), 133.9 (2C), 126.0 (2C), 125.7 (2C), 119.8 (2C), 116.6 (2C), 110.3 (2C), 108.9 (2C), 82.0 (2C), 49.7 (2C), 48.3 (2C). LCMS:

To an aluminum pan was charged with 14 grams of the. The aluminum pan was then put into a 150° C. vacuum oven to be melted and degassed for 1 hour. After degassing, the material was staged cured at 150° C. for 2 hours, 160° C. for 2 hours, 180° C. for 2 hours, and 200° C. for 2 hours. The DSC of the fresh made sample, and the DMA, TGA of one half of the cured product were determined. The other half of the cured product was further post cured at 250° C. for 3 hours and the DMA and TGA of this cured product were also determined. The results are shown below in Table 1 and 2.

Examples 12-17: Copolymerization of Phthalonitrile Monomer/Benzoxazine (Phenol-APA/TMBF-PN; Phenol-APA/FTMBF-PN; Phenol-APA/BisA-PN; Phenol-APA/BisC-PN; Phenol-APA/BisM-PN; Phenol-APA/BisP-PN)

To each of six 4 oz. glass jars was charged 20 grams of phenol 3-aminophenyl acetylene benzoxazine (Phenol-APA; example 1). The glass jar was then put into an 80° C. oven until the material had melted, and then, while stirring, 6 grams of compounds as described in example 3 and 7 were added to the glass jar, respectively. The resulting mixtures were stirred occasionally until the added material had dissolved in the melted benzoxazine up at a temperature at 95° C. (example 16, Phenol-APA/BisM-PN, with BisM-PN; example 7), 120° C. (Phenol-APA/TMBF-PN, example 12, with TMBF-PN example 3), 140° C. (Phenol-APA/FTMBF-PN; example 13, with FTMBF-PN, example 4); short time at 150° C. (Phenol-APA/BisP-PN, example 17, with BisP-PN, example 8) and 160° C. (Phenol-APA/BisA-PN & Phenol-APA/BisC-PN, examples 14, 15, with BiaA-PN & BisC-PN, examples 5 and 6), respectively. About 13 grams of the mixture was then transferred into an aluminum pan. After degassing at 85° C., the mixture was staged cured at 120° C. for 2 hours, 150° C. for 2 hours, 180° C. for 2 hours, and 200° C. for 2 hours, or 160° C. for 2 hours, 170° C. for 2 hours, 180° C. for 2 hours, and 200° C. for 2 hours. The DSC of the freshly made sample, and the DMA, TGA of one half of the cured product were determined. The other half of the cured product was further post cured at 250° C. or 260° C. for 3-4 hours and the DMA and TGA of this cured product were determined. The results are shown below in Table 1 and Table 2.

Example 18. Copolymerization of Phthalonitrile Monomer/Benzoxazine (Phenol-APA/FTMBF-PN)

To a 4 oz. of glass jar, was charged with 12 grams of phenol 3-aminophenyl acetylene benzoxazine (Phenol-APA; example 1). The glass jar was then put into an 80° C. oven until the material had melted, and then, while stirring, 2.4 grams of phthalonitrile made from furanyl-2,2′,6,6′-tetramethylbisphenol F (FTBMF-PN; example 5) were added to the glass jar. The resulting mixture was heated up gradually to 150° C. and stirred occasionally until the added material had dissolved in the melted benzoxazine. About 12.5 grams of the mixture was transferred into an aluminum pan. After degassing at 65° C., the mixture was staged cured at 120° C. for 2 hours, 150° C. 2 hours, 180° C. 2 hours, and 200° C. for 2 hours. The DSC of the fresh made sample, and the DMA, TGA of one half of the cured product were determined. The other half of the cured product was further post cured at 250° C. for 3 hours and the DMA and TGA of this cured product were also determined. The results are shown below in Table 1 and Table 2.

Example 19. Copolymerization of Phthalonitrile Monomer/Benzoxazine (Phenol-APA/FTMBF-PN)

To a 4 oz. of glass jar, was charged with 10.8 grams of phenol 3-aminophenyl acetylene benzoxazine (Phenol-APA, example 1). The glass jar was then put into an 80° C. oven until the material had melted, and then, while stirring, 5.38 grams of the phthalonitrile (FTMBF-PN, example 5) were added to the glass jar. The resulting mixture was heated up gradually to 150° C. and stirred occasionally until the added material had dissolved in the melted benzoxazine. About 12.5 grams of the mixture was transferred into an aluminum pan. After degassing at 65° C., the mixture was staged cured at 120° C. for 2 hours, 150° C. 2 hours, 180° C. 2 hours, and 200° C. for 2 hours. The DSC of the freshly made sample, and the DMA, TGA of one half of the cured product were determined. The other half of the cured product was further post cured at 250° C. for 3 hours and the DMA and TGA of this cured product were also determined. The results are shown below in Table 1 and table 2.

Example 20. Copolymerization of Phthalonitrile Monomer/Benzoxazine (Phenol-APA/BisM-PN)

To a 4 oz. of glass jar, was charged with 20 grams of phenol 3-aminophenyl acetylene benzoxazine (Phenol-APA, example 1). The glass jar was then put into an 80° C. oven until the material had melted, and then, while stirring, 10 grams of the bisphenol M-phthalonitrile (BisM-PN, example 7) were added to the glass jar until all dissolved (up to 130° C.). About 12.5 grams of the mixture was transferred into an aluminum pan. The mixture was staged cured at 140° C. for 2 hours, 180° C. 2 hours, and 220° C. for 3 hours. The DSC of the freshly made sample, and the DMA, TGA of one half of the cured product were determined. The other half of the cured product was further post cured at 260° C. for 4 hours and the DMA and TGA of this cured product were also determined. The results are shown below in Table 1 and table 2.

Example 21: Copolymerization of Phthalonitrile Monomer/Benzoxazine (Phenol-APA/TMBF-PN)

To a 4 oz. of glass jar, was charged with 21 grams of phenol 3-aminophenyl acetylene benzoxazine (Phenol-APA, example 1). The glass jar was then put into an 80° C. oven until the material had melted, and then, while stirring, 9 grams of the 2,2′,6,6′-tetramethylbisphenol F derived phthalonitrile (TMBF-PN, example 3) were added to the glass jar. The resulting mixture was heated up gradually to 150° C. and stirred occasionally until the added material had dissolved in the melted benzoxazine. About 12.5 grams of the mixture was transferred into an aluminum pan. The mixture was staged cured at 140° C. for 1 hours, 160° C. 2 hours, 180° C. 2 hours and 200° C. for 2 hours. The DSC of the freshly made sample, and the DMA, TGA of one half of the cured product were determined. The other half of the cured product was further post cured at 260° C. for 4 hours and the DMA and TGA of this cured product were also determined. The results are shown below in Table 1 and Table 2.

Example 22. Copolymerization of Phthalonitrile Monomer/Benzoxazine (AllylPh-APA/BisM-PN)

To a 4 oz. of glass jar, was charged with 20 grams of 2-allylphenol 3-aminophenyl acetylene benzoxazine (AllylPh-APA, example 2) and 6 grams of the bisphenol M-phthalonitrile (BisM-PN, Example 7). The glass jar was then put into an 80° C. oven. The oven was gradually heated up to 130° C., and the resulting mixture stirred occasionally until the added material had dissolved in the melted benzoxazine. About 12.5 grams of the mixture was transferred into an aluminum pan. After degassing at 85° C., the mixture was staged cured at 140° C. for 1 hours, 160° C. 2 hours, 180° C. 2 hours, and 220° C. for 3 hours. The DSC of the freshly made sample, and the DMA, TGA of one half of the cured product were determined. The other half of the cured product was further post cured at 260° C. for 3 hours and the DMA and TGA of this cured product were also determined. The results are shown below in Table 1 and Table 2.

Example 23. Copolymerization of Phthalonitrile Monomer/Benzoxazine (Allylph-APA/TMBF-PN)

To a 4 oz. of glass jar, was charged with 20 grams of 2-allylphenol 3-aminophenyl acetylene benzoxazine (AllylPh-APA, example 2), and then, while stirring, 6 grams of the TMBF-phthalonitrile (TMBF-PN, example 3,) were added to the glass jar. The glass jar was then put into an 80° C. oven. The oven was gradually heated up to 130° C., and the resulting mixture stirred occasionally until the added material had dissolved in the melted benzoxazine. About 12.5 grams of the mixture was transferred into an aluminum pan. After degassing at 85° C., the mixture was staged cured at 140° C. for 1 hours, 160° C. 2 hours, 180° C. 2 hours, and 220° C. for 3 hours. The DSC of the freshly made sample, and the DMA, TGA of one half of the cured product were determined. The other half of the cured product was further post cured at 260° C. for 3 hours and the DMA and TGA of this cured product were also determined. The results are shown below in Table 1 and Table 2.

Example 24: Copolymerization of Phthalonitrile Monomer/Benzoxazine (Phenol-APA/Phenol-FA/BisM-PN)

To a 4 oz. of glass jar, was charged with 10 grams of phenol 3-aminophenyl acetylene benzoxazine (Phenol-APA, example 1) and 10 g phenol furfuryl amine benzoxazine (Phenol-FA, example 9). The glass jar was then put into a 90° C. oven until the material had melted, and then, while stirring, 6.0 grams of the phthalonitrile derived from bisphenol M (BisM-PN, example 7) were added to the glass jar. The temperature was then raised to 130 Co. The resulting mixture was stirred occasionally until the added material had dissolved in the melted benzoxazine. After degassing at 100° C., the mixture was staged cured at 120° C. for 2 hours, 150° C. 2 hours, 180° C. 2 hours, and 200° C. for 2 hours. The DSC of the freshly made sample, and the DMA, TGA of one half of the cured product were determined. The other half of the cured product was further post cured at 250° C. for 3 hours and the DMA and TGA of this cured product were also determined. The results are shown below in Table 1 and Table 2.

Example 25: Copolymerization of Phthalonitrile Monomer/Benzoxazine (Phenol-APA/TDP-AN/BisM-PN)

To a 4 oz. of glass jar, was charged with 20 grams phenol 3-aminophenyl acetylene benzoxazine (Phenol-APA; example 1) and 10 grams of 4,4′-thiodiphenol aniline benzoxazine (TDP-AN; example 10). The glass jar was then put into a 90° C. oven until the material had melted, and then, while stirring, 10 grams of the bisphenol M phthalonitrile (BisM-PN, example 7) were added to the glass jar. The resulting mixture was stirred occasionally until the added material had dissolved in the melted benzoxazine. About 12.5 grams of the mixture was transferred into an aluminum pan. After degassing at 100° C., the mixture was staged cured at 120° C. for 2 hours, 150° C. 2 hours, 180° C. 2 hours, and 200° C. for 2 hours. The DSC of the freshly made sample, and the DMA, TGA of one half of the cured product were determined. The other half of the cured product was further post cured at 250° C. for 3 hours and the DMA and TGA of this cured product were also determined. The results are shown below in Table 1 and Table 2.

Examples 26: Copolymerization of Phthalonitrile Monomer/Benzoxazine (Phenol-APA/MT35700/TMBF-PN)

To a 4 oz. of glass jar, was charged 16 grams of phenol 3-aminophenyl acetylene benzoxazine (Phenol-APA, example 1). The glass jar was then put into a 110° C. oven to melt, and then, while stirring, 4.0 grams of the phthalonitrile derived from 2,2′,6,6′-tetramethylbisphenol F (TMBF-PN, example 3) were added to the glass jar. The resulting mixture was stirred occasionally until the added material had dissolved in the melted benzoxazine. Then 7 g of commercially available Araldite MT35700 (MT35700, bisphenol F/phenol aniline benzoxazine resin; obtained internally) was added until all melted together, about 12.5 grams of the mixture was transferred into an aluminum pan. The mixture was staged cured at 140° C. for 2 hours, 160° C. 2 hours, 180° C. 2 hours, and 200° C. for 2 hours. The DSC of the freshly made sample, and the DMA, TGA of one half of the cured product were determined. The other half of the cured product was further post cured at 250° C. for 4 hours and the DMA and TGA of this cured product were also determined. The results are shown below in Table 1 and Table 2.

Example 27: Copolymerization of Phthalonitrile Monomer/Benzoxazine (Phenol-APA/Phenol-FA/BP-FA/BisM-PN)

To a 4 oz. of glass jar, was charged with 5 grams of phenol 3-aminophenyl acetylene benzoxazine (Phenol-APA, example 1) and 5 g phenol furfuryl amine benzoxazine (Phenol-FA, example 9). The glass jar was then put into a 90° C. oven until the material had melted, and then, while stirring, 3.0 grams of the phthalonitrile derived from bisphenol M (BisM-PN, example 7) were added to the glass jar. Then, while stirring, 13 grams of the 4,4′-diphenol furfuryl amine benzoxazine (BP-FA, example 11) were added to the glass jar. The resulting mixture was stirred occasionally until the added material had dissolved in the melted benzoxazine. About 12.5 grams of the mixture was transferred into an aluminum pan. After degassing at 100° C., the mixture was staged cured at 120° C. for 2 hours, 150° C. 2 hours, 180° C. 2 hours, and 200° C. for 2 hours. The DSC of the freshly made sample, and the DMA, TGA of one half of the cured product were determined. The other half of the cured product was further post cured at 250° C. for 3 hours and the DMA and TGA of this cured product were also determined. The results are shown below in Table 1 and Table 2.

Example 28: Copolymerization of Phthalonitrile Monomer/Benzoxazine (Phenol-APA/TDP-AN/FTMBF-PN)

To a 4 oz. of glass jar, was charged with 20 grams benzoxazine and phthalonitriles mixture (Phenol-APA/FTMBF-PN; example 13). The glass jar was then put into a 110° C. oven until the material had melted, and then, while stirring, 7 grams of the 4,4′-thiodiphenol aniline amine benzoxazine (TDP-AN, example 10) were added to the glass jar. The resulting mixture was stirred occasionally until the added material melted. About 12.5 grams of the mixture was transferred into an aluminum pan. The mixture was staged cured at 140° C. for 2 hours, 160° C. 2 hours, 180° C. 2 hours, and 200° C. for 2 hours. The DSC of the freshly made sample, and the DMA, TGA of one half of the cured product were determined. The other half of the cured product was further post cured at 250° C. for 4 hours and the DMA and TGA of this cured product were also determined. The results are shown below in Table 1 and Table 2.

Example 29: Copolymerization of Phthalonitrile Monomer/Benzoxazine (Phenol-APA/FTMBF-PN/TMBF-PN)

To a 4 oz. of glass jar, was charged 20 grams previous made mixture of example (Phenol-APA/FTMBF-PN, example 13). The glass jar was then put into a 90° C. oven to melt, and then, while stirring, 4.0 grams of the phthalonitrile derived from 2,2′,6,6′-tetramethylbisphenol F (TMBF-PN, example 3) were added to the glass jar. The temperature of oven was raised to 150° C. gradually, and resulting mixture was stirred occasionally until the added material had dissolved in the melted benzoxazine. About 12.5 grams of the mixture was transferred into an aluminum pan. The mixture was staged cured at 150° C. for 1 hours, 160° C. 2 hours, 180° C. 2 hours, and 200° C. for 2 hours. The DSC of the freshly made sample, and the DMA, TGA of one half of the cured product were determined. The other half of the cured product was further post cured at 260° C. for 4 hours and the DMA and TGA of this cured product were also determined. The results are shown below in Table 1 and Table 2.

Example 30: Copolymerization of Phthalonitrile Monomer/Benzoxazine (Phenol-APA/BisM-PN/BisA-PN)

To a 4 oz. of glass jar, was charged 12 grams of phenol 3-aminophenyl acetylene benzoxazine (Phenol-APA, example 1). The glass jar was then put into a 130° C. oven to melt, and then, while stirring, 8.0 grams of the phthalonitrile derived from bisphenol-M (BisM-PN, example 7) were added to the glass jar. The resulting mixture was stirred occasionally until the added material had dissolved in the melted benzoxazine. Then 2 grams of bisphenol A derived phthalonitrile (BisA-PN, Example 5) was stirred in until dissolved. About 12.5 grams of the mixture was transferred into an aluminum pan. The mixture was staged cured at 140° C. for 2 hours, 160° C. 2 hours, 180° C. 2 hours, and 200° C. for 2 hours. The DSC of the freshly made sample, and the DMA, TGA of one half of the cured product were determined. The other half of the cured product was further post cured at 250° C. for 4 hours and the DMA and TGA of this cured product were also determined. The results are shown below in Table 1 and Table 2.

TABLE 1 Mixing temp. MP Onset peak Enthalpy Examples Component BOX:PN (° C.) (° C.) (° C.) (° C.) (J/g) Comp. Ex. 1 Ph-APA 1:0 53-55 235 245 876 Comp. Ex. 2 AllylPh-APA liquid 135 165 42 227 251 317 Comp. Ex 3 TMBF-PN 0:1 193 341 372 286 Comp. Ex 4 FTMBF-PN 0:1 207 316 338 231 Comp. Ex 5 BisA-PN 0:1 198 309 361 39 Comp. Ex 6 BisC-PN 0:1 209 305 326 83 Comp. Ex 7 BisM-PN 0:1 135 274 344 101 Comp. Ex 8 BisP-PN 0:1 202 292 346 57 Comp. Ex. 9 Phenol-FA 1:0 54-56 232 245 498 Comp. Ex. 10 TDP-AN 1:0 100 230 242 1428 Comp. Ex. 11 BP-FA 1:0 150 228 240 896 Ex. 12 Phenol-APA 10:3  120 228 241 728 TMBF-PN Ex. 13 Phenol-APA 10:3  150 230 243 707 FTMBF-PN Ex. 14 Phenol-APA 10:3  160 232 245 623 BisA-PN Ex. 15 Phenol-APA 10:3  160 230 245 615 BisC-PN Ex. 16 Phenol-APA 10:3  100 236 248 856 BisM-PN Ex. 17 Phenol-APA 10:3  150 231 246 750 BisP-PN Ex. 18 Phenol-APA 10:2  100 227 240 754 FTMBF-PN Ex. 19 Phenol-APA 10:5  110 225 240 596 FTMBF-PN Ex. 20 Phenol-APA 1:1 130 215 237 613 BisM-PN Ex. 21 Phenol-APA 7:3 150 230 243 716 TMBF-PN Ex. 22 AllylPh- 10:3  80 227 264 419 APA, BisM- PN Ex. 23 AllylPh- 10:3  130 226 265 478 APA, TMBF-PN Ex. 24 Phenol- 10:3  100 208 228 655 APA, Phenol-FA, BisM-PN Ex. 25 Phenol- 3:1 100 199 224 728 APA, TDP- AN, BisM- PN Ex. 26 Phenol- 3:1 110 226 241 520 APA, MT35700, TMBF-PN Ex. 27 Phenol- 23:3  100 204 228 537 APA, Phenol-FA, BP-FA, BisM-PN Ex. 28 Phenol- 3:1 110 221 236 221 APA, TDP- AN, FTMBF-PN Ex. 29 Phenol- ~3:2  150 228 244 625 APA, FTMBF-PN, TMBF-PN Ex. 30 Phenol- 6:5 130 217 238 446 APA, BisM-PN, BisA-PN

TABLE 2 Storage DMA Char 95% 90% Viscosity Modulus Tg Yield weight weight BOX:PN @75° C. @25° C. onset @800° C. retain retain Examples Component Ratio (centipoises) (MPa) (° C.) (%) (° C.) (° C.) Comp. Ex. 1 Phenol-APA 1:0 <50 4549 209 55.07 391 404 Comp. Ex. 1 1:0 3946 334 55.23 397 409 (w/Post Cure) Comp. Ex. 2 AllylPh-APA 1:0 <50 4280 105 41.15 411 422 Comp. Ex. 2 3991 NA 41.59 411 422 (w/Post Cure) Comp. Ex 3 TMBF-PN 0:1 solid 3687 >400  77.70 492 544 Comp. Ex 4 FTMBF-PN 0:1 solid Broken N/A 75.73 450 518 Comp. Ex 5 BisA-PN 0:1 solid 2479 >400  75.61 475 509 Comp. Ex 6 BisC-PN 0:1 solid Broken N/A 66.60 416 454 Comp. Ex 7 BisM-PN 0:1 solid 1033 133 64.19 450 477 Comp. Ex 8 BisP-PN 0:1 solid 509 260 71.65 468 497 Comp. Ex. 9 Phenol-FA 1:0 <50 4102 160 54.64 325 394 Comp. Ex. 9 3922   320.97 56.98 389 423 (w/Post Cure) Comp. Ex. 10 TDP-AN 1:0 Deformed N/A 40.12 310 325 Comp. Ex. 11 BP-FA 1:0 solid 3994 239 65.49 349 426 Comp. Ex. 11 4276 336 66.28 387 441 (w/Post Cure) Ex. 12 Phenol-APA 10:3  140 3958 185 69.98 426 466 TMBF-PN Ex. 12 3545 301 70.29 426 467 (w/Post Cure) Ex. 13 Phenol-APA 10:3  210 4249 215 69.73 430 464 FTMBF-PN Ex. 13 4191 290 69.54 418 457 (w/Post Cure) Ex. 14 Phenol-APA 10:3  220 4459 129 71.14 426 469 BisA-PN Ex. 14 4510 345 73.02 421 467 (w/Post Cure) Ex. 15 Phenol-APA 10:3  200 4917 150 74.24 419 464 BisC-PN Ex. 15 4009 326 74.17 427 466 (w/Post Cure) Ex. 16 Phenol-APA 10:3  90 3619 176 66.73 423 460 BisM-PN Ex. 16 3515 332 66.96 422 460 (w/Post Cure) EX. 17 Phenol-APA; 10:3  130 4175 157 66.39 418 449 BisP-PN Ex. 17 4550 333 68.37 414 452 (w/Post Cure) Ex. 18 Phenol-APA 10:2  150 4002 237 65.82 419 447 FTMBF-PN Ex. 18 3925 316 64.84 412 440 (w/Post Cure) Ex. 19 Phenol-APA 10:5  980 3608 202 71.67 436 471 FTMBF-PN Ex. 19 4438 262 71.69 431 471 (w/Post Cure) Ex. 20 Phenol-APA 1:1 1673 4947 219 71.40 438 482 BisM-PN Comp. Ex. 20 3425 316 71.60 438 482 (w/Post Cure) Ex. 21 Phenol-APA 7:3 360 4604 127 71.65 432 468 TMBF-PN Ex. 21 3997 345 71.70 427 465 (w/Post Cure) Ex. 22 Allylph- 10:3  109 3772  88 APA, BisM- PN Ex. 22 3489 354 61.95 428 444 (w/Post Cure) Ex. 23 Allylph- 10:3  60 3630 115 65.24 419 447 APA, TMBF- PN Ex. 23 3271 363 64.24 429 449 (w/Post Cure) Ex. 24 Phenol-APA, 10:3  88.5 4088 135 63.07 391 436 Phenol-FA, BisM-PN Ex. 24 3507 274 62.74 390 434 (w/Post Cure) Ex. 25 Phenol-APA, 3:1 144 4173 146 65.17 390 434 TDP-AN, BisM-PN Ex. 25 4023 308 64.84 402 442 (w/Post Cure) Ex. 26 Phenol-APA, ~6:1  913 4119 198 64.56 399 431 MT35700, TMBF-PN Ex. 26 4252 304 64.29 404 433 (w/Post Cure) Ex. 27 Phenol-APA, 23:3  4125 4261 191 64.86 360 427 Phenol-FA, BP-FA, BisM-PN Ex. 27 3167 274 63.70 375 430 (w/Post Cure) Ex. 28 Phenol-APA, ~5:1  480 4608 227 65.94 391 422 TDP-Aniline, FTMBF-PN Ex. 28 4054 294 66.10 394 425 (w/Post Cure) Ex. 29 Phenol-APA, ~3:2  4125 3761 137 76.89 425 492 FTMBF-PN, TMBF-PN Ex. 29 4439 322 74.20 433 479 (w/Post Cure) Ex. 30 Phenol-APA, 6:5 1620 4580 218 77.53 431 487 BisM-PN, BisA-PN Ex. 30 4477 316 72.33 436 483 (w/Post Cure)

Although making and using various embodiments of the present invention have been described in detail above, it should be appreciated that the present invention provides many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed herein are merely illustrative of specific ways to make and use the invention, and do not delimit the scope of the invention. 

1. A polymerizable thermosetting composition comprising (i) one or more acetylene-bearing benzoxazine compounds, and (ii) a phthalonitrile monomer.
 2. The polymerizable thermosetting composition according to claim 1, wherein the one or more acetylene-bearing benzoxazine compounds are represented by the following structure:

wherein: each of R₁, R₂, R₃, R₄, and R₅ is independently selected from a hydrogen atom, a substituted or unsubstituted C₁-C₂₀ alkyl group, a substituted or unsubstituted C₂-C₂₀ alkenyl group, a substituted or unsubstituted C₆-C₂₀ aryl group, a substituted or unsubstituted C₂-C₂₀ heteroaryl group, a substituted or unsubstituted C₄-C₂₀ carbocyclic group, a substituted or unsubstituted C₂-C₂₀ heterocyclic group, or a C₃-C₈ cycloalkyl group; b is an integer ranging from 1 to 4, wherein: when b is 1, Z is a hydrogen atom, a substituted or unsubstituted C₁-C₂₀ alkyl group, a substituted or unsubstituted C₂-C₂₀ alkenyl group, a substituted or unsubstituted C₆-C₂₀ aryl group, a substituted or unsubstituted C₂-C₂₀ heteroaryl group, a substituted or unsubstituted C₄-C₂₀ carbocyclic group, a substituted or unsubstituted C₂-C₂₀ heterocyclic group, or a C₃-C₈ cycloalkyl group; each R₁ is an alkynyl substituted C₁-C₂₀ alkyl group, an alkynyl substituted C₈-C₂₀ aryl group, an alkynyl substituted C₂-C₂₀ heteroaryl group, an alkynyl substituted C₄-C₂₀ carbocyclic group, an alkynyl substituted C₂-C₂₀ heterocyclic group, or an alkynyl substituted C₃-C₈ cycloalkyl group; when b is 2, Z is a direct bond or a substituted or unsubstituted C₁-C₂₀ alkyl group, a substituted or unsubstituted C₂-C₂₀ alkyl group, with aryl or heteroaryl bridge, a substituted or unsubstituted C₂-C₂₀ alkenyl group, a substituted or unsubstituted C₂-C₂₀ alkynyl group, a substituted or unsubstituted C₆-C₂₀ aryl group, a substituted or unsubstituted C₂-C₂₀ heteroaryl group, O, S, S═O, O=S═O, C═O, or C═CCl₂; and when b is 3 or 4, Z is a substituted or unsubstituted C₁-C₂₀ alkyl group, a substituted or unsubstituted C₂-C₂₀ alkyl group, with aryl or heteroaryl bridge, a substituted or unsubstituted C₂-C₂₀ alkenyl group, a substituted or unsubstituted C₂-C₂₀ alkynyl group, a substituted or unsubstituted C₆-C₂₀ aryl group, a substituted or unsubstituted C₂-C₂₀ heteroaryl group; and each R₆ is an alkynyl substituted C₁-C₂₀ alkyl group, an alkynyl substituted C₈-C₂₀ aryl group, an alkynyl substituted C₂-C₂₀ heteroaryl group, an alkynyl substituted C₄-C₂₀ carbocyclic group, an alkynyl substituted C₂-C₂₀ heterocyclic group, or an alkynyl substituted C₃-C₈ cycloalkyl group.
 3. The polymerizable thermosetting composition according to claim 1, wherein the phthalonitrile monomer is one or more compounds having the formula

wherein each of R₁ to R₁₄ is independently selected from a hydrogen atom, a substituted or unsubstituted C₁-C₂₀ alkyl group, a substituted or unsubstituted C₂-C₂₀ alkenyl group, a substituted or unsubstituted C₂-C₂₀ alkynyl group, a substituted or unsubstituted C₆-C₂₀ aryl group, a substituted or unsubstituted C₂-C₂₀ heteroaryl group; and Z is selected from a direct bond, a substituted or unsubstituted C₁-C₂₀ alkyl group, a substituted or unsubstituted C₂-C₂₀ alkyl group with aryl or heteroaryl bridge, a substituted or unsubstituted C₂-C₂₀ alkenyl group, a substituted or unsubstituted C₂-C₂₀ alkynyl group, a substituted or unsubstituted C₆-C₂₀ aryl group, a substituted or unsubstituted C₂-C₂₀ heteroaryl group, O, S, S═O, O=S═O, C═O, C(═O)O, or C═CCl₂, or a polymer chain containing oxygen in each repeating unit of the polymer chain.
 4. The polymerizable thermosetting composition according to claim 1, further comprising at least one of a monofunctional benzoxazine, a multifunctional benzoxazine and a mixture thereof.
 5. A thermoset polymer obtained by curing the thermosetting composition according to claim
 1. 6. A process for producing a composite article comprising contacting a layer of reinforcement fibers with the polymerizable thermosetting composition according to claim 1 to coat and/or impregnate the reinforcement fibers; and curing the coated and/or impregnated reinforcement fibers to produce the composite article.
 7. A method for producing a composite article in a RTM system comprising the steps of: a) introducing a fiber preform comprising reinforcement fibers into a mold; b) injecting the polymerizable thermosetting composition according to claim 1 into the mold, c) allowing the thermosetting composition to impregnate the fiber preform; d) heating the resin impregnated preform for a period of time to produce an at least partially cured solid article; and optionally e) subjecting the partially cured solid article to additional heat.
 8. A method for producing a composite article in a VaRTM system comprising the steps of: a) introducing a fiber preform comprising reinforcement fibers into a mold; b) injecting the thermosetting composition according to claim 1 into the mold; c) reducing the pressure within the mold; d) maintaining the mold at about the reduced pressure; e) allowing the thermosetting composition to impregnate the fiber preform; f) heating the resin impregnated preform to produce an at least partially cured solid article; and optionally g) subjecting the at least partially cured solid article to additional heat. 